CN105322207B - A kind of phosphorous heteropoly acid positive electrolyte for all-vanadiumredox flow battery and its application - Google Patents
A kind of phosphorous heteropoly acid positive electrolyte for all-vanadiumredox flow battery and its application Download PDFInfo
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- CN105322207B CN105322207B CN201410367895.2A CN201410367895A CN105322207B CN 105322207 B CN105322207 B CN 105322207B CN 201410367895 A CN201410367895 A CN 201410367895A CN 105322207 B CN105322207 B CN 105322207B
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Abstract
The present invention relates to a kind of phosphorous heteropoly acid positive electrolyte for all-vanadiumredox flow battery and its application, phosphorous heteropoly acid additive in positive electrolyte for all-vanadiumredox flow battery be present, the phosphorous heteropoly acid is phosphotungstic acid, phosphomolybdic acid, phosphorus niobic acid, the one or two or more kinds of phosphorus tantalic acid；Concentration of the phosphorous heteropoly acid in the aqueous solution of anode electrolyte is 10‑3Mmol/L~0.1mol/L.The phosphorous heteropoly acid that the present invention uses can effectively suppress battery and run caused severe capacity fade problem under the high temperature conditions, realize the stable operation of battery as anode electrolyte.Preparation technology of the present invention is simple to operate, energy-conserving and environment-protective, cost is low while can realize the stable operation of electrolyte in the battery.
Description
Technical field
The present invention relates to the electrolyte of all-vanadium flow battery technical field, more particularly to a kind of full vanadium of phosphorous heteropoly acid
Fluid cell electrolyte.
Background technology
, can be again with continuous exhausted and people's environmental protection consciousness the continuous enhancing of fossil energy in worldwide
Raw energy source utilizing electricity generating techn is increasingly favored by people.Regenerative resource mainly includes wind energy, solar energy, biomass energy, sea
Ocean can wait, and they are generally converted to electric energy use.And these renewable energy power generations are influenceed tool by conditions such as region, meteorologies
There is obvious discontinuous, unstability.In order to smooth and stablize the generating output of regenerative resource and solve to generate electricity and electricity consumption
Time difference contradiction, improve power quality and electric network reliability, it is necessary to develop high-efficiency energy-storage technology.All-vanadium liquid flow energy storage battery (VFB)
It is securely and reliably, environment-friendly due to power system capacity and power is adjustable independently of each other, response is rapid, have extended cycle life, Yi Wei
The outstanding advantage such as shield and regeneration and turn into renewable energy power generation, power network peak load shifting, is met an urgent need and the scale such as stand-by station is stored up
One of most promising technology in energy.
The critical material of all-vanadium liquid flow energy storage battery mainly includes pole dual-pole board, film and electrolyte.All-vanadium liquid flow energy storage
The research of battery critical material, especially improving stability, durability and the research for reducing cost etc. of critical material
Just it is particularly important.Electrolyte solution is the important component of all-vanadium flow battery, and its concentration and volume directly determines
The capacity of battery.Therefore, the stability of electrolyte directly influences the stability of all-vanadium flow battery.Due to all-vanadium flow electricity
Pond electrolyte solution circulates in systems always, once there are the phase transformations such as precipitation, deposition or gasification, can cause liquid flow conduits
With the blocking of internal battery pack pipeline, system operation is influenceed, it is therefore necessary to ensure that being electrolysed liquid energy in the process of running keeps high living
Property and high stability.Further, since solubility of the vanadium ion in sulfuric acid is limited, when the concentration of pentavalent vanadium ion is more than
During 1.8mol/L or when operation temperature is higher than 50 DEG C, anode electrolyte is also easy to produce Precipitation in charging process, to a certain degree
On limit the raisings of system energy densities, how to improve energy density, and ensure that its stabilization in cell operation is deposited
It is being urgent problem to be solved.The problem of being separated out for electrolyte solution, universal thinking are added less in electrolyte solution
The additive of amount carrys out stable electrolyte solution, it is stabilized at higher concentrations.
Studies have reported that, using phosphorus tungsten vanadium series heteropoly acid as a kind of catalytic activity material of new flow battery
(H.D. Pratt Iii, T.M.Anderson, Dalton Transactions 2013,42,15650-15655.), illustrates this
Class material has certain electro-chemical activity.But because heteropoly acid is molten in sulfuric acid supporting electrolyte as active material in itself
Xie Du is extremely limited, and the energy density of battery is relatively low.And the efficiency for the flow battery for assembling such material as electrolyte
It is relatively low.Accordingly, it is considered to using a small amount of heteropoly acid as the electrolysis additive of all-vanadium flow battery, the oxidation of original vanadium is being kept
On the premise of reduction is to electrochemical reaction, the stability and electricity of electrolyte are improved by changing the active force between additive and vanadium
Chemical property.
The content of the invention
Present invention aims at solve the above problems, there is provided a kind of all-vanadium flow battery positive pole electricity of phosphorous heteropoly acid
Liquid is solved, to reach the purpose of all-vanadium flow battery efficient stable operation.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of phosphorous heteropoly acid positive electrolyte for all-vanadiumredox flow battery, exists in positive electrolyte for all-vanadiumredox flow battery
Phosphorous heteropoly acid additive, the phosphorous heteropoly acid are phosphotungstic acid, phosphomolybdic acid, phosphorus niobic acid, one kind of phosphorus tantalic acid or two kinds
More than, preferred phosphotungstic acid；Concentration of the phosphorous heteropoly acid in the aqueous solution of anode electrolyte is 10-3Mmol/L~
0.1mol/L。
The concentration of vanadium oxygen root is 0.5~5mol/L in the aqueous solution of anode electrolyte, and the concentration of sulfate radical is 1~6mol/
L。
The concentration of vanadium oxygen root is 1~3mol/L in the aqueous solution of the anode electrolyte, and sulfate concentration is 2~4mol/
L。
Concentration of the phosphorous heteropoly acid in anode electrolyte is 0.01mmol/L~0.05mol/L.
Vanadium oxygen root includes VO in the aqueous solution of anode electrolyte2+、VO2 +、V2O3 4+、VO2SO4 -；The aqueous solution of anode electrolyte
Middle sulfate radical includes SO4 2-And HSO4 -。
Anode electrolyte as all-vanadium flow battery is used in all-vanadium flow battery；
The all-vanadium flow battery is made with metal class electrode or carbon class electrode (carbon paper, carbon cloth, carbon felt, CNT)
For positive pole and negative material, with perfluorosulfonic acid type PEM, partially fluorinated film, non-fluorine ion exchange membrane or compound ion
Exchange membrane is barrier film.
Vanadium ion includes V in the all-vanadium flow battery electrolyte liquid2+, V3+；Sulfuric acid in the aqueous solution of electrolyte liquid
Root includes SO4 2-And HSO4 -。
Main component suitable for the electrolyte of vanadium redox battery of the present invention is higher valence state (four, pentavalent) vanadium oxygen root-sulfuric acid body
System.
The beneficial outcomes of the present invention are as follows：
Present invention uses phosphorous heteropoly acid as anolyte solution additive, the coordination of pentavalent vanadium can be obviously improved
Environment, improves the high high-temp stability of anode electrolyte, and effectively improves battery capacity in long-term cyclic process and keep
Rate, realize the long-term stable operation of battery.Preparation technology of the present invention is simple to operate, energy-conserving and environment-protective, cost is low while can ensure
Battery chronically efficient stable can be run.
Brief description of the drawings
Fig. 1 is that the nmr spectrum of pentavalent vanadium and blank pentavalent vanadium that phosphotungstic acid is added in embodiment 1 contrasts.
Fig. 2 is as the electrolyte of additive and the cyclic voltammetry curve of blank electrolysis liquid in embodiment 3 containing phosphotungstic acid.
Fig. 3 is the cycle performance of battery figure of the additive of phosphotungstic acid containing very small amount in embodiment 4.
Fig. 4 is the anode electrolyte of the additive of phosphotungstic acid containing very small amount and the blank without any additive in embodiment 5
Capacity attenuation comparison diagram during anode electrolyte assembled battery.
Embodiment
The following examples are the further explanations to the present invention, rather than limit the scope of the present invention.
Embodiment 1：
To 1.0mol/L VO2 +With 3mol/L H2SO4Blank anode electrolyte in, be slowly added to phosphotungstic acid, make phosphorus tungsten
Concentration of the acid in the aqueous solution of anode electrolyte is 0.3mmol/L, respectively to blank sample and the pentavalent vanadium sample of addition additive
Product carry out NMR tests, by nuclear magnetic resoance spectrum Fig. 1 analysis can draw, after the addition of phosphotungstic acid, script blank pentavalent vanadium from
The unimodal left and right of nuclear-magnetism corresponding to son generates new nuclear-magnetism peak respectively, illustrates to occur between additive phosphotungstic acid and pentavalent vanadium ion
Interaction, change the coordination environment of pentavalent vanadium.
Embodiment 2
1.8mol/L pentavalent vanadium solutions are prepared using electrolysis, phosphotungstic acid is added into 10mL pentavalent vanadium solutions respectively, makes
Concentration of the phosphotungstic acid in the aqueous solution of anode electrolyte is 0.016mol/L, 0.03mol/L and 0.04mol/L phosphotungstic acids,
Stirred after being sufficiently mixed, and be placed in 80 DEG C of water-bath and heat together with blank pentavalent vanadium sample, observe the shape of solution
State, investigate influence of the addition of different phosphotungstic acids for pentavalent vanadium heat endurance.
Influence situation table of the different content additive of table 1. for electrolyte stability
| The amount (mol/L) of additive | Stabilization time (h) |
| 0 | 0.5 |
| 0.016 | 1 |
| 0.03 | 2.5 |
| 0.04 | 3 |
The mechanism of action of additive is the emphasis of numerous research work, but because experimental period is longer, enhances experiment and see
The difficulty examined.Therefore for the ease of investigating influence of the phosphotungstic acid for pentavalent vanadium heat endurance in a short time, using embodiment 2
In extreme condition under 80 DEG C of heating water bath carry out heat endurance experiment.When additive adds electrolyte, electrolyte
Color is changed immediately, is changed into claret from orange-yellow, illustrates vanadium ion and phosphotungstic acid interaction shape in electrolyte
Into certain new state.When pentavalent vanadium is in high temperature bath environment, blank pentavalent vanadium solution generates red soon
V2O5Precipitation.And add the stabilization time of the pentavalent vanadium of phosphotungstic acid on this condition and extend with the increase of addition, illustrate phosphorus
The addition of wolframic acid has significantly inhibitory action for the Precipitation of electrolyte.This is due to the addition of a small amount of phosphotungstic acid, with
Pentavalent vanadium ion in electrolyte is complexed to form new state after, significantly reduce V2O5Evolution reaction, it is achieved thereby that electrolysis
The presence steady in a long-term of liquid at high temperature.Operation of the result for electrolyte under high temperature has positive role, advantageously ensures that
Steady in a long-term operation of the all-vanadium flow battery in hot environment.
Embodiment 3
Tested by three-electrode system testing device on CHI electrochemical workstations and obtain blank anode electrolyte (0.05M
Tetravalence vanadium V (IV)+0.05M pentavalent vanadiums V (V)+3M H2SO4) and the additive containing 0.3mmol/L electrolyte cyclic voltammogram,
As shown in Figure 2.Figure it is seen that a small amount of addition of phosphotungstic acid, can significantly improve V (IV)/oxygen of M (V) electricity between
Change reducing activity, anode and cathode peak current is obviously improved.Cyclic voltammetry curve is contrasted simultaneously, it is found that a small amount of of electrolysis additive adds
Add, have little to no effect the redox reversible of electrolyte.
Embodiment 4
To 60mL anode electrolytes (1.6mol/L VOSO4+3mol/L H2SO4) in add 0.3mmol/L phosphotungstic acids it is molten
Liquid, electrolyte to be measured is made after stirring and being completely dissolved.Anolyte is used as by the use of the electrolyte containing phosphotungstic acid
Liquid, with 1.6 mol/L V3++3mol/L H2SO4Make electrolyte liquid, assemble all-vanadium liquid flow energy storage monocell.Wherein, battery every
Film is Nafion115 (Dupont), and film effective area is 48cm2, electrode is activated carbon-fiber felt, and bipolar plates are graphite cake, and electric current is close
Spend for 80mA cm-2.Monocell carries out constant current charge-discharge at normal temperatures, blanking voltage 1.0-1.55V, thus obtains such as Fig. 3 institutes
Circulating battery stability in 100 circulations shown.As can be seen from Figure, due to the phase interaction between phosphotungstic acid and vanadium ion
With the monocell for adding minimal amount of phosphotungstic acid is less efficient in circulation initial voltage.But with the progress of circulation, voltage effect
Rate gradually steps up, and energy efficiency also significantly improves therewith.After treating that battery performance is stable, coulombic efficiency 94.4%, voltage effect
Rate is 88.0%, the electricity being not added with energy efficiency 83.2%, respectively higher than the same terms after the battery stabilization of phosphotungstic acid
Press efficiency (86.0%) energy efficiency (81%).
Embodiment 5
To 60mL anode electrolytes (1.6mol/L VOSO4+3mol/L H2SO4) in add 0.3mmol/L phosphotungstic acids it is molten
Liquid, electrolyte to be measured is made after stirring and being completely dissolved.Respectively with electrolyte and blank electrolysis containing phosphotungstic acid
Liquid is as anode electrolyte, 1.6mol/L V3++3mol/L H2SO4Electrolyte liquid is both functioned as, assembles all-vanadium liquid flow energy storage list
Battery.Wherein, battery diaphragm is Nafion115 (Dupont), and film effective area is 48cm2, electrode is activated carbon-fiber felt, bipolar plates
For graphite cake, current density is 80mA cm-2.Monocell carries out constant current charge-discharge at normal temperatures, blanking voltage 1.0-1.55V,
Thus battery capacity attenuation curve in 130 circulations as shown in Figure 4 is obtained.As can be seen from Figure, with not adding additive
Battery compare, due to the interaction between phosphotungstic acid and vanadium ion, add minimal amount of phosphotungstic acid and can slow down battery and exist
Capacity attenuation in cyclic process.Therefore stability when phosphotungstic acid can be obviously improved electrolyte longtime running, battery is improved
Capability retention, realize that all-vanadium flow battery is more stably run.
Claims (6)
- A kind of 1. application of positive electrolyte for all-vanadiumredox flow battery, it is characterised in that：In positive electrolyte for all-vanadiumredox flow battery Phosphorous heteropoly acid additive be present, the phosphorous heteropoly acid is phosphotungstic acid；The phosphotungstic acid is in the water-soluble of anode electrolyte Concentration in liquid is 10-3Mmol/L~0.1mol/L.
- 2. application according to claim 1, it is characterised in that：The concentration of vanadium oxygen root is in the aqueous solution of anode electrolyte 0.5~5mol/L, the concentration of sulfate radical is 1~6mol/L.
- 3. application according to claim 1 or 2, it is characterised in that：Vanadium oxygen root in the aqueous solution of the anode electrolyte Concentration is 1~3mol/L, and sulfate concentration is 2~4mol/L.
- 4. application according to claim 1 or 2, it is characterised in that：The phosphorous heteropoly acid is in anode electrolyte Concentration is 0.01mmol/L~0.05mol/L.
- 5. the application of anode electrolyte according to claim 2, it is characterised in that：Vanadium oxygen in the aqueous solution of anode electrolyte Root includes VO2+、VO2 +、V2O3 4+、VO2SO4 -；Sulfate radical includes SO in the aqueous solution of anode electrolyte4 2-And HSO4 -。
- 6. according to the application described in claim 1-5, it is characterised in that：Anode electrolyte as all-vanadium flow battery is used for complete In vanadium flow battery；The all-vanadium flow battery using metal class electrode or carbon class electrode as positive pole and negative material, with Perfluorosulfonic acid type PEM, partially fluorinated film, non-fluorine ion exchange membrane or cluster ion exchange membrane are barrier film；It is described complete Vanadium ion includes V in vanadium flow battery electrolyte liquid2+And V3+；Sulfate radical includes SO in the aqueous solution of electrolyte liquid4 2-With HSO4 -；The carbon class electrode includes one kind in carbon paper, carbon cloth, carbon felt or CNT.
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| GB2549708B (en) * | 2016-04-21 | 2019-01-02 | Siemens Ag | A reduction-oxidation flow battery |
| CN106299434A (en) * | 2016-11-11 | 2017-01-04 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of electrolyte of vanadium redox battery containing inorganic molybdate and vanadium cell |
| CN111180775A (en) * | 2018-11-13 | 2020-05-19 | 陕西华银科技股份有限公司 | Novel all-vanadium redox flow battery positive electrode electrolyte and application thereof |
| CN112908723A (en) * | 2021-03-08 | 2021-06-04 | 广西师范大学 | Heteropolyacid aqueous electrolyte for carbon-based super capacitor |
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| CN101728560A (en) * | 2009-04-10 | 2010-06-09 | 承德万利通实业集团有限公司 | Method for preparing vanadium redox battery negative pole electrolyte |
| CN102881931A (en) * | 2012-09-26 | 2013-01-16 | 清华大学 | Phosphorus-containing all-vanadium redox flow battery anode electrolyte |
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| CN101728560A (en) * | 2009-04-10 | 2010-06-09 | 承德万利通实业集团有限公司 | Method for preparing vanadium redox battery negative pole electrolyte |
| CN102881931A (en) * | 2012-09-26 | 2013-01-16 | 清华大学 | Phosphorus-containing all-vanadium redox flow battery anode electrolyte |
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